Synthetic resins



Patented Mar. 2 1937 SYNTHETIC RESINS Richard T. Ubben, Wilmington, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 24, 1934, Serial No. 727,283

10 Claims.

adapted particularly for coatings, and comprising a hydrogenated aldehyde-polynuclear phenol resin together with a drying oil or other esterlike body having drying properties.

2 Other objects and advantages of the invention will be apparent from the following specification in which its preferred embodiments are described.

In accordance with the invention it has been found that new plastic bodies, having properties adapting them for important uses in the arts, are obtained by hydrogenating aldehyde-polynuclear phenol resins, especially those resins which before hydrogenation are of the heat-hardenable type. The term polynuclear phenol", as used herein, designates monohydric or polyhydric phenols containing at least two carbocyclic nuclei, at least one of which is aromatic. may contain other substituent groups in addition to the phenolic hydroxyl groups and in the case of polyhydric polynuclear phenols, the hydroxyl groups may be in the same or in different arematic nuclei. The term heat-hardenable has reference, as will be understood, to the relative ease with which the resinous condensation products of polynuclear phenols and aldehydes may be rendered insoluble and infusible by suitable heat-treatment.

For a proper appreciation of the objects, importance, and b c nature of this invention, it is necessary that he following background of the art be clearly comprehended. Common vamishmaking procedure, prior to the advent of synthetic resins, and also to a large extent since their development has consisted simply in heating a natural resin such as ordinary rosin with a natural vegetable drying oil such as linseed or China-wood oil. when and as synthetic resins became available, the art immediately attempted to substitute them for the natural resin. However (it has been 5 learned thru experience that synthetic resins gen- The polynuclear phenols (01. zoo-4) eraliy, because they are very different from natural resins in physical properties and chemical constitution and behavior, cannot be used to replace rosin in varnish-marking. The art then began to search for methods specific to utilizing, 5 not only each class of resin, but also the several members of each class. Because of their importance and early development, phenol-formaldehyde condensation products have received a full share of attention. One result of such research has been the development of numerous methodsbased largely on auxiliary ingredients-which purport to be suitable for making homogeneous varnishes from phenol-aldehyde resins general- 1y. Another result has been the selection'of those particular phenol-aldehyde condensation products which are most suited for making varnishes by the old, well-established method of simply heating with the drying oil. Selections of the latter nature have led tocertain generalizationszgo regarding that chemical structure of the phenols which produces oil-solubility. A very important and basic contribution to the art was made by Honel (U. S. 1,800,296) who discovered that the phenols from which the aldehyde condensation product was made should have not more than two unsubstituted positions ortho and/or para to the phenolic hydroxyl group or groups. The explanation of this is that a condensation product prepared from such a phenol has little if any tendency on heat-treatment to be converted to an infusible, insoluble resin; such a requisite is obviously necessary because otherwisev an inhomogeneous mass would be obtained on heating with the oil. Now the Honel patent was concerned only with non-resinous phenol-aldehyde condensation products, which are not the. typedesired by the varnish trade. The next major discovery was made by Brubaker (U. S. appl. Ser. No. 662,001, filed March 21, 1933) who learned that certain further structural requirements were necessary if the phenol-formaldehyde condensation product was to be converted first} to the hard, brittle (though still non-heatrharde'nable) type of product desired by the varnish trade. Thus the field of suitable reslns'was narrowed a second time.

A parallel problem which has confronted the phenol-aldehyde resin and varnish arts is the development of resins and resin varnishes which are not subject to discolorationon exposure to light in film form." It has been fairly definitely determined that this defect-whichis notorious with ordina y phenol-formaldehyde inherent in the phenols. An obvious solution of this problem is therefore the'proper selection'of the phenol, and work along these lines by numerous investigators has demonstrated rather definitely that discoloration is more or less decreased, sometimes almost wholly prevented, if 5 the phenol from which the resin is made has all the positions para to phenolic hydroxyl blocked by a tertiary aliphatic carbon atom. This is supposed to be due to the prevention of a quinoidlike degradation of the phenol to colored byproducts.

' From a consideration of the above, it will be readily admitted that a very fine selection of phenols, representing a very narrow portion of the field, must be made for synthesizing aphenoll5 aldehyde resin having Physical properties acceptable to the varnish trade, and having chemical properties which permit it to be blended by common methods with drying oils to form varnish bases of reasonable resistance to discolora tion. Moreover, as in the case of all chemical generalizations, there are isolated unexplainable anomalies which narrow the field even more.

There is still another problem in the preparation of phenol-aldehyde varnish resins which has never been solved to any satisfactory extent. Rosin is soluble in hydrocarbon solvents and the latter very economical type of solvent is accordingly suitable for rosin-drying oil varnishes. However, phenol formaldehyde resins are not generally soluble in hydrocarbons, and the varnish bases made therewith accordingly require large proportions of expensive oxygenated solvents.

The present invention, directed in particular to formaldehyde-polynuclear phenol resins be- 35 cause of their current interest and availability and also their ability to be readily hydrogenated, presents a satisfactory solution to all the above problems. More specifically, the advantages of this invention for particular classes of aldehydepolynuclear phenol resins are:

I.Heat-hardenable resins are rendered A. Non-heat-hardenable B. Oil-soluble C. Discoloration-resistant .(where initially subject to discoloration) D. Soluble'in hydrocarbons II.Non-heat-hardenable resins are rendered A. Oil-soluble (where initially oil-insoluble) B. Discoloration-resistant (where initially subject to discoloration) C. Soluble in hydrocarbonsior more soluble,

if already soluble to some extent) I1I.--Non-heat-hardenable, oil-soluble resins are rendered 55 A. Discoloration-resistant (where initially subject to discoloration) B. Soluble in hydrocarbons (or more soluble,

if already soluble to some extent) IV.-Non-heat-hardenable, oil-soluble, discol- 60 oration-t resins are rendered A. Soluble in hydrocarbons (or more soluble,

if already soluble to some extent) Summing up, the present invention improves.

formaldehyde-polynuclear phenol resins in one or more of the following respects: (1) increase in oil-solubility, (2) in resistance to discoloration, (3) in solubility in hydrocarbons, and (4) conversion of heat-hardenable resins to a non-heathardenable form. Finally, the invention involves a radical and basic departure from all prior methods and efforts of the art because it comprises a treatment of the preformed resin, and not just another method of making the resin or another selection of ingredients therefor.

In practising the invention the aldehydephenol is subjected to liquid phase hydrogenation in the presence of a hydrogenation catalyst. Generally it is preferred to hydrogenate the resin in the form of a solution in an organic solvent, e. g., an alcohol, ether, or ester. The quantity and nature of the solvent used may vary with the particular resin to be hydrogenated but in general it is preferable to use suilicient solvent to eilect complete solution of the resin. As an alternative. but less desirable method, the molten resin may be hydrogenated without use of added solvent.

To the resin in suitable liquid state a hydrogenation catalyst (e. g., nickel supported on kieselguhr) is added, the mixture is placed in an autoclave equipped with agitating means, and subjected to contact with hydrogen, under suitable temperature and pressure conditions, until the desired degree of hydrogenation is accomplished. The catalystis removed by filtration and the resin recovered by evaporation of solvent. The extent of hydrogenation efiected in each case will depend upon the degree to which it is desired to modify the properties of the original resin, any substantial addition of hydrogen being effective in producing to some extent the improvement in properties hereinbefore referred to.

Hydrogenation catalysts suitable for use in the process include the metals of the iron and platinum groups. The catalysts may be made by any of the mthods well known to the art, and may be employed in the form of a colloidal dispersion in an organic solvent or, preferably, in conjunction with an inert support, e. g., kieselguhr,

pumice, active carbon, silica gel, or the like. The preferred catalyst is finely powdered nickel and may be prepared in an active form by a number of methods, but the preferred procedure-consists in reducing with hydrogen compounds of nickel containing oxygen, e. g., the carbonate, oxides, hydroxides, etc., salts of an inorganic acid, e. g., chromic acid, vanadic acid, tungstic acid, etc. Suitable temperatures for the reduction of such nickel compounds are found in the range 250- 500" C. When reducing chromates by heat alone or together with hydrogen, chromites are formed and these serve as the support for the hydrogenating catalyst. Especially useful for the purpose is finely divided nickel distributed on kieselguhr. An alternative preferred catalyst may be prepared by the digestion of a nickel-aluminum alloy with caustic soda according to the process described in U. 8. Patent 1,628,190. The platinum metals have the advantage of more effectively accelerating the desired reaction at atmospheric pressure.

While the invention in its broad aspects is not limited to the employment of any specific conditions of operation, the hydrogenation is preferably effected at a temperature within the range of -225" C. and a pressure within the range of -4000 lbs. per sq. in. Especially good results have been obtained at ISO- C. and 1500-2500 lbs. per sq. in.

As previously indicated, the invention broadly involves the preparation of improved resinous bodies by hydrogenation of aldehyde-polynuclear phenol resins. Another feature of the invention, however, is the application of these products to the manufacture of compositions including said products and one or more ester-like bodies having drying properties. The hydrogenated aldehyde-polynuclear phenol resins, whether initially (i. e. before hydrogenation) of the heat-hardenwas prepared from the foregoing hydrogenatedable or non-heat-hardenable type, are found to be compatible with oils, especially drying oils (e. g. China-wood oil, linseed oil, sunflower seed oil, oiticica oil, perilla oil, walnut oil, safllower seed oil, etc.) and other ester-like bodies having drying properties. In the last named category are included polyhydric alcohol-polycarboxylic acid resins modified with drying oils such as the above or with the acids derived from their saponification. The latter resins are well-known in the art and need no further description. The ester-like bodies having drying properties are in general characterized by low acidity and the property of drying, as films, by absorption of oxygen from the atmosphere.

The followingexamples are given as illustrating preferred methods of practicing the invention, altho it is to be understood that the invention is not limited thereto:

Example 1.This example illustrates the preparation and hydrogenation of a typical heathardenable, oil-insoluble aldehyde-polynuclear phenol resin obtainable by interreaction of di(4- hydroxyphenyl)dimethylmethane and formaldehyde.

' Production of the resin To grams of sodium hydroxide (2 mols) dissolved in 1000 grams of distilled water is added with stirring 228 grams of di(4hydroxyphenyl) dimethylmethane (1 mol.) and 200 grams of a 37% formaldehyde solution (2.5 mols) and the mixture is allowed to stand at room temperature for three days. The solution is then neutralized with dilute hydrochloric acid. The oily layer is washed three times with warm water, transferred to a shallow tray, and vacuum dried at 55-60" C. for 5 hours. The product obtained is a light ambercolored resin soluble in alcohol, limitedly soluble in ester solvents, and insoluble in hydrocarbon solvents, and fatty oils. Thisresin is readily converted to the infusible, insoluble state by heattreatment above C.

Hydrogenation of the resin To 196 grams of a 50% ethyl alcohol solution of the di(4-hydroxypheny1) dlmethylmethane-formaldehyde resin prepared as described above is added 10 grams of a nickel-on-kieselguhr catalyst, and the mixture is placed in an autoclave equipped for agitation. A hydrogen pressure of 2000 lbs. per sq. in. is applied and the temperature is brought gradually to 180-200" C., where it is maintained for 5.5 hours. Hydrogen absorption begins at about -150 C., reaches a maximum at about 180 C., and finally decreases toward the end of the period of heating. At the completion of the run the catalyst is removed by filtration, and the resin recovered by evaporation of the solvent. The product obtained is a light ambercolored resin, readily soluble in aromatic hydrocarbon and ester solvents, compatible with drying oils, e. g., China-wood oil, and is not convertible to the insoluble, infusible stage even by heat-treatment at about C. for three hours. The unhydrogenated resin, on the other hand, is insoluble in aromatic hydrocarbons, limitedly soluble in esters, incompatible with oils, and is converted to the insoluble, infusible stage in a few minutes by heat-treatment at 150 C.

Vamish manufacture An oleoresinous varnish of 25 gallons oil length resin as follows:

Parts by weight Hydrogenated resin 34 Raw China wood oil 66 Total- 100 cordance with the invention are, forexample,

those that may be produced by reaction of formaldehyde with one of the following polynuclear phenols: p,p'-dihydroxydiphenyl, di(4-hydroxyphenyl) cyclohexane, p,p'dihydroxybenzophenone, p,p'dihydroxydiphenyl ether, beta-di(4- hydroxyphenyl) naphthane, 1,1 di(4 hydroxyphenyl) 4 methylcyclohexane, di(4 hydroxynaphthyl) methane, and ar-tetrahydro-betanaphthol.

Example 2.The practise of the invention may be further illustrated by the hydrogenation of a resin obtainable by condensation of p-hydroxydiphenyl and formaldehyde, this being an example of a non-heat-hardenable aldehyde-polynuclear phenol resin. It is a. hard, clear, light colored,

brittle material, soluble in aromatic hydrocarbons and in esters, and compatible with oils. However, oleoresinous varnishes or cellulose derivative compositions containing the resin discolor badly when thin films thereof are exposed to light, This defect, as will be readily admitted by the art, is so serious as almost completely to preclude the use of the oil or cellulose derivative-resin compositions in the formulation of varnishes (of enamels containing light-colored pigments), which in film form are not subject to after-yellowing. This defect is overcome by hydrogenating the resin as in the following paragraph.

To one hundred grams of the aforesaid resin dissolved in 150 grams of butyl acetate is added 10 grams of a nickel-on-kieselguhr catalyst. The mixture is placed in a shaking autoclave and agitated for 6 hours at 200 C. under a pressure of 2000 pounds per square inch. The catalyst is then filtered off, and the resin recovered by evaporation of the solvent.

Altho the hydrogenated resin has the same physical appearance as the unhydrogenated product (like the-latter material it is compatible in 1:1 ratio with organic cellulose esters and ethers, e. g., ethyl cellulose, benzyl cellulose, crotyl cellulose, cellulose propionate, cellulose isobutyrate, etc.) films of cellulose derivative or oleoresinous coatings prepared from the hydrogenated resin show practically no discoloration on exposure to light. Such an oleoresinous varnish may be made as follows:

Varnish manufacture The ingredients are mixed in the cold, heated to 232 C. in 25 minutes, and held at that temperature for 15 minutes longer, whereupon a clear, light amber-colored varnish is obtained. The varnish is removed from the fire, and cut with a solvent mixture consisting of equal parts of solvent naphtha and turpentine substitute. To the varnish solution thus obtained is added a suflicient amount of cobalt linoleate drier solution to give 0.01% cobalt, based on the weight of the oil.

The above varnish shows practically no afteryellowing when exposed in thin films to light. The varnish is also of lighter color, and has a lower viscosity at the same solids content than a varnish containing the unhydrogenated resin.

The hydrogenated resins produced in accordance with the invention may be combined either with drying oils or with organic cellulose derivatives, e. g. organic esters and ethers, especially ethyl cellulose and benzyl cellulose, to give highly useful coating compositions. Compatibilities with nitrocellulose are, however, limited. The following example is illustrative of a lacquer containing a cellulose derivative in combination with a hydrogenated aldehyde-polynuclear phenol resin.

Films cast from the above lacquer are clear, have excellent oil and water-resistance, and are superior in their resistance to discoloration when exposed to light, as compared with similar films containing the unhydrogenated resin. The ethyl cellulose of the above example may be replaced by other organic cellulose derivatives.

Plastic compositions may be made by suitable variation of proportions, e. g., the hydrogenated resin of Example 2, three parts; ethyl cellulose,

ten parts; dibutyl phthalate, two parts. This mixture can be made into a molding powder by the usual methods. Fillers can, of course, be added.

Other aldehyde-polynuclear phenol resins that may be hydrogenated in practising the invention are, for example, those synthesized from formaldehyde and any one of the following phenols: di(4-hydroxy 3 methylphenyl) dimethylmethane, di(4-hydroxy-3-chlorphenyl)dimethylmethane, di(4-hydroxynaphthyl) methylethyimethane, di(4-hydroxy 3 methylphenyl) ethylmethane, 1,1-di (4 hydroxy -3- methylphenyl) cyclohexane, di (2-hydroxy-5-methylphenyl) dimethylmethane, di(4 hydroxy-3 methylphenyl)phenylmethane, beta-naphthol, alpha-naphthol, hydroxyxanthones, p-cyclohexylphenol, and p-(4-methylcyclohexyl) phenol.

Resins made from polynuclear phenols containing sulfur should generally be avoided since sulfur poisons most hydrogenation catalysts. Resins from such phenols as di(4-hydroxyphenyl) sulfide and sulfone can, however, be hydrogenated with sulfur-insensitive catalysts.

Altho the preferred aldehyde for the synthesis of the resins used in the practise of this invention is formaldehyde, it may be replaced wholly or in part by such materials as hexamethylenetetramine, methylene chloride, methylal, paraformaldehyde, furfural, benzaldehyde, etc.

It will be apparent from the foregoing that the novel compositions obtained by hydrogenation of aldehyde-polynuclear phenol resins represent an important advance in the art particularly in view of their improved light stability, compatibility with oils and adaptability to the manufacture of oleoresinous varnishes. It is to be understood that they may be employed in a variety of ways in the manufacture of plastic and coating compositions, in which connection they may be blended, with other materials, by heating, solvents or other means known to the art, and either with or without cellulose derivatives or the mentioned ester-like bodies having drying properties. Other materials with which the hydrogenated resins may be blended include other synthetic resins and resin-forming materials, e. g., coumaroneindene resins, amine-aldehyde resins, polyvinyl resins, polyacrylic and polymethacrylic resins, polyhydric alcohol-polycarboxylic acid resins; bitumens, e. g., asphalt; natural and synthetic waxes, e. g., beeswax, candelilla wax, montan wax, lauryl stearate, and hydrogenated castor oil; non-drying and semi-drying vegetable and animal oils and fats, e. g., castor oil, olive oil, cocoanut oil, cottonseed oil, etc.

To the hydrogenated alhehyde-polynuclear phenol resins, combined with cellulose derivatives and/or ester-like bodies having drying properties and/or one or more of the above enumerated substances, may be added pigments, solvents, plasticizers, anti-oxidants, fillers, lakes, etc., as needed and desired and in accordance with methods well known in the art.

In addition to the particular use as non-discoloring coating compositions the hydrogenated aldehyde-polynuclear phenol resins of this invention per se or combined with any one of the above enumerated materials may be used as molding plastics; as impregnating and coating agents for paper, cloth, porous stone, rubberized fabrics, etc.; as the sandwiching material or adhesive therefor in the manufacture of shatterproof glass; as adhesives, cements, and sealing waxes for general use; and as binding agents for mica, asbestos, and the like in the manufacture of insulating materials; in the manufacture of sheet and tubular products; as a binder for cotton flock in the manufacture of suede-like materials, etc.

Altho in the foregoing specification there have been indicated various proportions of ingredients, temperatures, pressures, etc., it is to be understood that these and other details may be varied within comparatively wide limits without departure from the invention and without sacrifice of any of its substantial benefits and advantages.

I claim:

1. The process which comprises reacting an aldehyde-polynuclear phenol resin with hydrogen in the presence of a hydrogenating catalyst at a temperature within the range of 140-225" C. and a pressure within the range of 150-4000 lbs. per sq. in.

2. The process which comprises reacting an aldehyde-polynuclear phenol resin with hydrogen in the presence of a nickel catalyst at a temperature within the range of 140-225" C. and a pressure within the range of 150-4000 lbs. per sq. in.

3. The process which comprises contacting hydrogen with an aldehyde-polynuclear phenol resin, dissolved in an organic solvent, in the presence of a hydrogenating catalyst at a temperature within the range of 140-225 C. and a pressure within the range of 150-4000 lbs. per sq. in.

4. The process of converting a heat-hardenable aldehyde-polynuclear phenol resin to a relatively non-heat-hardenable resin which comprises contacting the heat-hardenable aldehyde-polynuclear phenol resin with hydrogen in the presence of a hydrogenating catalyst, at ,a temperature within the range of 140-225 C., and at a pressure within the range of 150-4000 lbs. per sq. in., until substantial hydrogenation is effected.

5. The process which comprises contacting hydrogen, at a pressure of about 2000 lbs. per sq. in. for about 5 hours at 180-200" C., with a ethyl alcohol solution of di(4-hyd.roxylphenyl) dimethylmethane-formaldehyde resin in the presence of a nickel-on-kieselguhr catalyst, while submitting the mixture to agitation; thereafter removing the catalyst by filtration and recovering the hydrogenated resin by evaporation of the solvent.

6. An artificial body capable of forming a homogeneous product when heated with a drying oil and obtainable by hydrogenation of an aldehyde-polynuclear phenol resin at a temperature within the range 01 -225 C. and a pressure within the range of -4000 lbs. per sq. in.

'7. A composition of matter comprising the product obtainable byheating China-wood oil with a hydrogenated di(4-hydroxyphenyl). dimethylmethane-formaldehyde resin obtained according to the process of claim 1.

8. A composition of matter comprising a hydrogenated aldehyde-polynuclear phenol resin obtained according to the process of claim 1 and at least one film-forming material selected from the group consisting of cellulose esters, cellulose ethers, vegetable drying oils, and polyhydric a1- cohol-polycarboxylic acid resins containing drying oil acid radicals.

9. A composition of matter comprising a vegetable drying oil and. a hydrogenated aldehydepolynuclear phenol resin obtained according to the process of claim 1.

10. A composition of matter comprising the product obtainable by heating a vegetable drying oil and a hydrogenated aldehyde-polynuclear phenol resin obtained according to the process of claim 1.

RICHARD '1. UBBEN. 

